Vibronic And Spin Angular Momentum In Rotationally Resolved Spectra Of Jahn-teller Active Molecules

Sharma, Ketan

Permalink

https://hdl.handle.net/2142/111039 Copy

Description

Title

Vibronic And Spin Angular Momentum In Rotationally Resolved Spectra Of Jahn-teller Active Molecules

Author(s)

Sharma, Ketan

Contributor(s)

• Stanton, John F.
• Miller, Terry A.

Issue Date

2021-06-23

Keyword(s)

Theory and Computation

Abstract

Effects due to vibronic and spin angular momentum have long been observed in rotationally resolved spectra of Jahn-Teller active molecules. The breakdown of the Born-Oppenheimer approximation in these molecules leads to complications in their vibronic spectra. The molecular picture is further complicated due to the coupling of spin angular momenta with rotational and vibronic angular momentum. Values of these coupling constants have been determined by many high resolution rotationally resolved spectroscopic experiments. However, the presence of a conical intersection in the adiabatic potential energy surfaces has made getting a reliable quantum chemistry calculation of these terms challenging. In this talk we present methods that have been developed to make first principles calculations of vibronic angular momenta and Coriolis coupling constants from quantum chemistry. Further methods have been developed to calculated spin related terms (spin-orbit quenching and spin rotation coupling), using ab initio methods and model vibronic hamiltonian. We report a comparision of calculations of these parameters with corresponding results determined from high resolution spectroscopy for molecules like methoxy radical and cyclopentadienyl radical.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Permalink

http://hdl.handle.net/2142/111039

DOI

10.15278/isms.2021.WK13

Owning Collections